KR20190003569A - Silane-containing high modulus urethane adhesive - Google Patents

Abstract

The moisture curable one-component adhesive contains an isocyanate-terminated prepolymer, a low molecular weight polyisocyanate compound, a hydrolyzable mercaptosilane, a urethane catalyst, and a carbon black filler. The adhesive exhibits a good combination of high modulus, good hydrolysis and thermal stability, and high sag resistance.

Description

Silane-containing high modulus urethane adhesive

The present invention relates to a new high modulus urethane adhesive composition containing silane. The present invention also relates to a novel process for preparing such high modulus urethane adhesive compositions.

Urethane adhesive compositions are used in many industrial applications. In the transportation industry, urethane adhesive compositions are used to adhere glass objects such as window shields or backlight windows to the bodywork structure. In order to provide adequate rigidity and thus better NVH performance to the car, it is desirable to use such a composition in which a urethane adhesive composition having high modulus properties is cured in situ. In addition to the properties of high modulus, it is also desirable that such urethane adhesive compositions are usable and pumpable at room temperature without any or many additional heating. Moreover, it is also desirable that the urethane adhesive can be adhered to the glass frit with good hydrolysis and thermal stability.

Presently, high modulus urethane adhesive compositions can be achieved through the use of light polymeric resins, i. E. Acrylic resins and / or crystalline polyester resins. Such existing compositions typically have a high viscosity and are likely to require heating during manufacture and application.

The present invention provides a new adhesive composition that exhibits similar or higher modulus and elongation when silane is introduced into the mixer rather than introduced during synthesis of the prepolymer resin. It is surprising to find that an adhesive composition containing mercaptosilane has excellent performance in sag resistance. It is also surprising to find that when the high modulus adhesive composition is prepared in the presence of mercaptosilane, the adhesive composition exhibiting excellent hydrolysis and thermal stability of glass adhesion is achieved.

 In one aspect, the adhesive composition of the present invention comprises a urethane prepolymer resin, a reactive silane, a polyisocyanate having a functionality of greater than 2, at least one catalyst for the reaction of an isocyanate with a hydroxyl group; And carbon black fillers.

The adhesive composition of any of the aforementioned aspects of the present invention can be dispensed at room temperature with little or no heat, with high modulus properties and sag resistance and durable adhesion with good hydrolysis and thermal stability.

In a particular aspect,

a) an isocyanate-terminated prepolymer having a free isocyanate group and an isocyanate equivalent of 840 to 5,000;

b) 0.1 to 6 parts by weight of at least one polyisocyanate compound, per 100 parts by weight of the moisture-curable adhesive composition, having an isocyanate equivalent of 300 or less and a number average number of isocyanate functionality of 2.5 or more;

c) from 0.1 to 4 parts by weight of at least one hydrolyzable organosilane, per 100 parts by weight of the moisture-curable adhesive composition, of mercaptosilane having one mercapto group and at least one hydrolyzable silane group;

d) at least one urethane catalyst, and

e) a carbon black filler.

The present invention also relates to

A) forming an isocyanate-terminated prepolymer;

B) mixing the isocyanate-terminated prepolymer with at least one hydrolysable silane, and thereafter

C) combining at least one polyisocyanate compound having an isocyanate equivalent of not more than 300, a urethane catalyst and carbon black with a mixture of said isocyanate-terminated prepolymer and said at least one hydrolyzable silane. And a method for producing an adhesive composition.

The present invention also relates to

A) forming an isocyanate-terminated prepolymer;

B) mixing the isocyanate-terminated prepolymer with at least one polyisocyanate compound having an isocyanate equivalent of not more than 300; And thereafter

C) combining the at least one hydrolysable silane, urethane catalyst and carbon black with a mixture of said isocyanate-terminated prepolymer and at least one hydrolyzable silane.

In another aspect, the present invention relates to a process for making a composition comprising contacting a moisture-curable adhesive composition according to the present invention with one or more substrates, contacting the two or more substrates with an adhesive composition disposed on an adhesive line between the substrates, Thereby forming an adhesive layer adhered to the substrate at the adhesive line.

The prepolymer has an isocyanate equivalent of 840 or greater, corresponding to an NCO content of 5% by weight. The isocyanate equivalent of the prepolymer may be at least 1050 (NCO content 4%) or higher, 1400 (NCO content 3%) or higher or 1680 (NCO content 2.5%) or higher, for example 10,000 (NCO content 0.42% (NCO content 0.5%) or less, 7000 (NCO content 0.6%) or less, or 5000 (NCO content 0.84%) or less. The prepolymer equivalents and molecular weights are measured according to the procedures disclosed in U.S. Patent No. 5,922,809, column 12, lines 50 to 64, incorporated herein by reference.

The prepolymer is the reaction product of at least one polyol and at least one polyisocyanate having an isocyanate equivalent weight of 250 or less. The polyol or mixture of polyols (if used) preferably has a hydroxyl equivalent of at least? 200 (equivalent to a hydroxyl number of 280). The hydroxyl equivalent may be 500 (OH = 112) or more, 800 (OH = 70) or 1000 (OH is 56) or more, 4750 OH of 22.4) or less. The polyol equivalents are determined by titration. Equivalents to the polyol mixture are determined by titrating the mixture, or titrating the individual components and measuring the number average. When a mixture of polyols is used, it is preferred that at least one component of the mixture has a hydroxyl equivalent of 500 to 3000, in particular 800 to 2000.

The polyol or mixture of polyols (if used) has a number average nominal hydroxyl functionality of 1.5 or more or 1.8. The hydroxyl functionality may be 2.0 or more, 2.2 or more, and may be 4 or less, 3.5 or less, 3.0 or less, or 2.7 or less. The " nominal " functionality of the polyol is the calculated number of hydroxyl groups per molecule based on the starting material used to produce the polyol. In the case of polyether polyols, the nominal functionality is the average number of hydroxyl groups per molecule of initiator compound or compounds used to prepare the polyether polyol. As is well known, the actual functionality of the polyether polyols tends to be somewhat lower than the nominal functionality due to the side reactions that occur during the polymerization of the alkylene oxide.

In a preferred embodiment, the polyol is a polymer mixture comprising at least one nominally bifunctional polyol and at least one nominally trifunctional polyol. Such a mixture may have an average hydroxyl functionality of 2.2 to 2.7.

Polyols useful for preparing the prepolymer include those disclosed in Wu Semantic Patent No. 6,512,033, column 4, lines 10 to 64, incorporated herein by reference. These include, for example, polyether polyols, polyester polyols, poly (alkylene carbonate) polyols, hydroxyl-containing polythioethers, polymer polyols (dispersions of any of the polyols described above) There is a mixture of two or more.

Polyether polyols are the preferred type. The polyether polyol may be, for example, tetrahydrofuran, and / or one or more alkylene oxides such as ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, ≪ / RTI > or mixtures of any two or more thereof. Particularly preferred polyether polyols are homopolymers of 1,2-propylene oxide, random copolymers of at least 50% by weight of 1,2-propylene oxide with ethylene oxide, or block copolymers of 1,2-propylene oxide and ethylene oxide . Such polyether polyols can be capped with ethylene oxide to produce more reactive primary hydroxyl groups.

The polyisocyanate used to prepare the prepolymer is one or more compounds having two or more isocyanate groups and an isocyanate equivalent of 300 or less, preferably 75 to 250. The polyisocyanate preferably has an average isocyanate functionality of from 2 to 4, more preferably from 2 to 3.5, even more preferably from 2 to 2.5 and even more preferably from 2 to 2.2. The polyisocyanate may be an aliphatic, alicyclic, araliphatic, heterocyclic or aromatic polyisocyanate, or a mixture of any two or more thereof. Aromatic polyisocyanates are particularly preferred for the preparation of prepolymers. Mixtures of at least one aromatic polyisocyanate and a minor amount (e.g., up to 20% by weight, based on the total weight of the polyisocyanate used to prepare the prepolymer) may be used.

Examples of aromatic polyisocyanates include diphenylmethane diisocyanate (MDI) and polymethylene polyphenyl isocyanate, polymer MDI (PMDI, a mixture of diphenylmethane diisocyanate and polymethylene polyphenylisocyanate), tetramethylxylene diisocyanate, and toluene di Isocyanates, any of which may be modified to include buret, alonate, urea, carbamate, isocyanurate or carbodiimide groups.

Examples of aliphatic polyisocyanates include isophorone diisocyanate, 1,6-hexamethylene diisocyanate, bis (4-isocyanatocyclohexyl) methane (H ₁₂ MDI) and trimethylhexamethylene diisocyanate, Any can be modified to include buret, alonfonate, urea, carbamate, isocyanurate or carbodiimide groups.

The prepolymer is reacted with the polyol (s) and the polyisocyanate in a ratio to provide an isocyanate group of greater than 1, preferably 1.5 to 2.5 or 1.5 to 2.1, equivalents per equivalent of hydroxyl groups, and until the hydroxyl groups are consumed Lt; / RTI > The prepolymer may be prepared by any suitable method, such as bulk polymerization and solution polymerization. The reaction is preferably carried out under anhydrous conditions, preferably under an inert atmosphere, such as a nitrogen blanket. The reaction is preferably carried out at a temperature of from about 0 캜 to about 150 캜, more preferably from about 25 캜 to about 90 캜. The reaction is generally carried out until the residual isocyanate content reaches a constant value indicating that all of the hydroxyl groups have been consumed. The reaction can be carried out in the presence of a urethane catalyst as described below.

The prepolymer may be prepared in the presence of a plasticizer as described below. In some embodiments, the amount of plasticizer present during preparation of the prepolymer is selected such that the resulting mixture of prepolymer and plasticizer has a preferred viscosity. Preferably, the resulting mixture of prepolymer and plasticizer has a Brookfield viscosity of 6,000 centipoise or greater, or about 8,000 centipoise or greater, and 30,000 centipoise or less, or 20,000 centipoise or less. Brookfield viscosity is measured in a Model DV-E Brookfield viscometer or equivalent device with RV spindle # 5 at a speed of 5 revolutions per second and a temperature of 25 캜.

The prepolymer comprises at least 30%, at least 35%, at least 40%, at least 50%, or at least 55% of the total weight of the adhesive composition. Up to 95%, up to 90%, up to 75% or up to 70% of the total weight of the adhesive composition.

In some embodiments, at least a portion of the isocyanate-terminated prepolymer is a polyester-containing prepolymer produced by the reaction of an excess of polyisocyanate with at least one polyester polyol that is solid at room temperature. Preferably, the polyester polyol has a melting point of at least about 40 占 폚, at least about 45 占 폚, and most preferably at least about 50 占 폚, at least about 85 占 폚, and more preferably at least about 70 占 폚. Preferably, the polyester-containing prepolymer comprises at least about 0.5 wt.% Or at least about 1 wt.% Of the adhesive composition weight, for example up to about 5 wt.% Or up to about 3 wt.% Can be configured. Preferred polyester polyols are prepared from linear diacids and linear diols. A more preferred disaccharide is adipic acid. More preferred diols are C2 to C6 diols such as butanediol, pentanediol and hexanediol. Preferred polyester polyols are available from Evonik under the trade names Dynacoll (TM) and the names 7360, 7330 and 7381. Polyester polyol isocyanate prepolymers can be prepared using the methods and isocyanates described above.

The adhesive composition of the present invention further comprises 0.1 to 6 parts by weight of at least one polyisocyanate compound having an isocyanate equivalent of 300 or less per 100 parts by weight of the adhesive composition. This additional polyisocyanate has an isocyanate functionality of at least 2.5, preferably at least 2.7, more preferably at least 2.9. The isocyanate action may be, for example, 4 or less or 3.5 or less. The average isocyanate action is measured according to paragraph 12, line 65 to line 13, line 26 of U.S. Patent No. 5,922,809, incorporated herein by reference.

Preferred additional polyisocyanates include polymeric MDI, polymethylene polyphenyl isocyanate, trimerized aromatic and / or aliphatic polyisocyanates such as partially or fully trimerized MDI, partially or fully trimerized toluene diisocyanate, and partially or fully Hexamethylene diisocyanate fully trimerized. At least a portion of the additional polyisocyanate is preferably an aliphatic polyisocyanate. Additional polyisocyanates may be, for example, partially or fully trimerized 1,6-hexamethylene diisocyanate, or aromatic polyisocyanates such as polymethylene polyphenyl isocyanate or PMDI and mixtures thereof.

The adhesive composition of the present invention further comprises at least one hydrolyzable mercaptosilane. The mercaptosilanes are characterized by having one, preferably exactly one mercapto group, and at least one, preferably from one to three, and more preferably from one to two hydrolysable silane groups.

The hydrolyzable silane group is a group containing a silicon atom and at least one hydrolysable substituent bonded to the silicon atom. The hydrolyzable silane group may contain one, two or three hydrolysable substituents. The silicon atom is bonded to the remainder of the compound (and particularly to the mercapto group) via a non-hydrolyzable bond.

The hydrolysable substituent reacts with water to remove the substituent and produce silanol moiety -Si-OH, which can be further reacted to form a siloxane bond (-Si-O-Si-) have. Hydrolyzable substituents include halogen, especially chlorine; Alkoxy groups, especially C _1-6 alkoxy and especially methoxy and ethoxy; Phenoxy or a ring-substituted phenoxy group, an acyloxy group such as acetoxy; Trialkylsiloxy groups which may be substituted in at least one of the alkyl groups, such as trimethylsiloxy and triethylsiloxy; Triphenylsiloxy, which may be substituted in one or more of the phenyl rings; Alkenyloxy groups such as isopropenyloxy; And ketoximato groups such as dimethyl ketoximoato, diethyl ketoximoato, dicyclohexylketoxomato and methylethyl ketoximoato.

Examples of the hydrolyzable silane group include trichlorosilyl, methyldichlorosilyl, dimethylchlorosilyl, phenyldichlorosilyl, (trimethylsiloxy) dimethylsilyl, trimethoxysilyl, triethoxysilyl, methyldiethoxysilyl, methyldimethoxysilyl , Dimethylmethoxysilyl, diethylmethoxysilyl, phenyldimethoxysilyl, trimethylsiloxymethylmethoxysilyl, trimethylsiloxydiethoxysilyl, methyldiacetoxysilyl, phenyldiacetoxysilyl, triacetoxysilyl, trimethyl (Dimethylketoxomato) methylsilyl, bis (cyclohexylketoxomato) methylsilyl, bis (diethylketoxomato) trimethylsiloxysilyl, bis (dimethylketoxomato) methylsilyl, trimethylsiloxyacetoxysilyl, bis Methylethylketoxomato) methylsilyl, tris (acetoxymato) silyl, and methylisopropenyloxysilyl. Preferred hydrolyzable silane groups are trialkoxysilyl groups such as trimethoxysilyl and triethoxysilyl.

Particularly preferred mercaptosilanes are mercaptoalkyl (trialkoxy) silanes or mercaptoalkylmethyl (dialkoxy) silanes such as gamma-mercaptopropyltri (methoxy) silane or gamma-mercaptopropylmethyl (dimethoxy) silane .

The adhesive contains 0.1 to 4 parts by weight of mercaptosilane per 100 parts by weight of the adhesive composition. The mercaptosilane may constitute, for example, preferably 0.2 wt% or more, 0.3 wt% or more, or 0.5 wt% or more of the adhesive composition. The mercaptosilane may constitute 3.0 wt% or less, 2.0 wt% or less, or 1.5 wt% or less of the adhesive composition.

The adhesive composition of the present invention may contain one or more additional hydrolyzable organosilanes, which do not contain a mercapto group, such as one or more epoxy silanes, acrylic silanes, isocyanatosilanes, and other hydrolysable silanes containing at least one hydrolysable silane group, May be further included. Such hydrolyzable organosilanes are disclosed in US Patent Application Publication 2002/0100550, paragraphs 0043 to 0047 and 0055 to 0065, incorporated herein by reference. More specific examples include bis- (gamma-trimethoxysilylpropyl) amine, gamma-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -gamma- aminopropyltrimethoxysilane, gamma- glycidoxypropyl Trimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, and gamma-isocyanatopropyltrimethoxysilane.

 The adhesive composition also contains one or more urethane catalysts, that is, materials that catalyze the reaction of isocyanate moieties with water and / or hydroxyl, mercapto or amino groups. Suitable catalysts include, for example, metal catalysts such as metal chelates, carboxylates and organometallic compounds, as well as tertiary amines and mixtures of any two or more thereof. Preferred metal catalysts include tin carboxylates, organotin compounds and tin alkanoates. Mixtures of tertiary amines and organometallic compounds are preferred. Suitable organometallic compounds include organotin compounds such as alkyl tin oxide, tin alkanoate, dialkyl tin dicarboxylate, dialkyl tin dimercaptanoate, and dialkyl tin mercaptide. Tin metal alkanoates include tin octoate, bismuth octoate or bismuth neodecanoate. Preferred examples of dialkyltin dicarboxylate catalysts include 1,1-dimethyl tin dilaurate, 1,1-dibutyl tin diacetate, 1,1-dimethyl tin dimaleate and dimethyl tin dineodecanoate . Preferred metal alkanoates include bismuth octoate or bismuth neodecanoate. Preferably, the metal catalyst (s) is present in an amount of at least about 60 ppm, more preferably at least 120 ppm, based on the weight of the adhesive composition. Preferably, the metal catalyst constitutes 1.0 wt% or less, more preferably 0.5 wt% or less, or 0.1 wt% or less of the adhesive composition.

Preferred tertiary amine catalysts are those selected from the group consisting of dimorpholinodialkylether, di ((dialkylmorpholino) alkyl) ether, bis- (2-dimethylaminoethyl) ether, triethylenediamine, pentamethyldiethylenetriamine, N-dimethylcyclohexylamine, N, N-dimethylpiperazine, 4-methoxyethylmorpholine, N-ethylmorpholine and mixtures thereof. A preferred dimorpholonodialkyl ether is dimorpholonodiethyl ether. The preferred di ((dialkylmorpholino) alkyl) ether is (di- (2- (3,5-dimethylmorpholino) ethyl) -ether). The tertiary amine can constitute, for example, not less than 0.01% by weight, not less than 0.05% by weight, not less than 0.1% by weight, or not less than 0.2% by weight, for example not more than 2.0% by weight, not more than 1.75% 1.0% by weight or less, or 0.5% by weight or less.

In some embodiments, the amount of catalyst (s) is selected so that the adhesive composition has a working time of at least 6 minutes, preferably at least 10 minutes. The working time is the period of time after exposure to 23 ° C / 50% relative humidity conditions until the composition becomes unable to adhere to the substrate. Preferably, the compositions of the present invention are formulated to provide a working time of at least about 6 minutes, and more preferably at least about 10 minutes. Preferably, the working time is about 40 minutes or less, more preferably about 30 minutes or less.

The composition of the present invention also includes carbon black. The carbon black used in the present invention may be a conductive carbon black, which is not specifically treated (surface treated or oxidized) to be non-conductive. At least one non-conductive carbon black may be used with the conductive carbon black.

Examples of useful commercially available carbon black products are RAVEN ^TM 790, RAVEN ^TM 450, RAVEN ^TM 500, RAVEN ^TM 430, RAVEN ^TM 420, RAVEN ^TM 410, RAVEN ^TM 1040 and RAVEN ^TM 1060 carbon black, all available from Colombian , CSX (TM), Monarch ( ^TM) and Elftex (TM) carbon black available from Cabot Corporation, and Printex (TM) carbon black available from Degussa.

The preferred carbon black exhibits an oil absorption of at least 80, preferably at least 90, and more preferably at least 95 cm ³ dibutyl phthalate per 100 g of carbon black as determined according to ASTM D-2414-09. In addition, the carbon black preferably has an iodine value of at least 80. [ The iodine value is measured by ASTM D1510-11.

The adhesive composition may contain, for example, 10% by weight or more, 12% by weight or more, or 15% by weight, based on the total weight of the adhesive composition. The adhesive composition may contain up to 35 wt%, 30 wt% or 25 wt% carbon black, based on the total weight of the composition.

In addition to the materials described above, the adhesive composition of the present invention may contain a variety of optional ingredients.

The compositions of the present invention preferably comprise one or more plasticizers to modify the rheological and viscosity properties of the adhesive composition to the desired concentration. Suitable plasticizers should be water-free, inert to isocyanate groups, and compatible with the prepolymer (i. E., Not phase separated from this at room temperature). Suitable plasticizers include linear and branched alkyl phthalates such as diisononyl phthalate, dioctyl phthalate and dibutyl phthalate, partially hydrogenated terpenes commercially available as " HB-40 ", trioctyl phosphate, epoxy plasticizer, toluene- Methyl-2-pyrrolidinone and toluene, alkylbenzoates, soybean oil methyl esters, dialkyl benzoates of K-Flex ™, castor oil or rapeseed oil, Methyl methyl esters, alkyl sulfonic acid esters such as Mesmoll ^TM from LANXESS Deutschland GmbH.

The amount of the plasticizer in the adhesive composition of the present invention may be, for example, 1% by weight or more, 5% by weight or more, or 10% by weight or more, based on the total weight of the adhesive composition. The plasticizer is preferably present in an amount of up to 40% by weight or up to 30% by weight on the same basis. Most or all of the plasticizers are preferably introduced during the preparation of the prepolymer.

The adhesive composition of the present invention may further comprise one or more additional particulate fillers, for example, clay, calcium oxide, calcium carbonate, ground glass, ceramics such as boron nitride, metals, crosslinked organic polymers, lignocellulose powder, dry silica . Preferred fillers include calcium carbonate. The calcium carbonate particles may not be treated or may be surface-modified by treatment with a chemical such as an organic acid or an organic acid ester. In some embodiments, the calcium carbonate comprises at least 1 wt%, at least 2 wt%, at least 3 wt%, or at least 5 wt% of the total weight of the adhesive composition. The calcium carbonate may constitute, for example, not more than 30% by weight, not more than 20% by weight, not more than 15% by weight or not more than 10% by weight on the same basis.

The adhesive composition of the present invention may further comprise at least one moisture stabilizer that functions to inhibit progress and prevent premature crosslinking. Among such moisture stabilizers are diethyl malonate, alkyl phenol alkylates, paratoluene sulfonic acid isocyanates, benzoyl chloride and orthoalkyl formates. Such stabilizers are preferably used in an amount of at least 0.1 wt.%, At least 0.5 wt.%, Or at least 0.8 wt.%, At most 5.0 wt.%, At most 2.0 wt.%, Or at most 1.4 wt.%, Based on the total weight of the adhesive composition do.

The adhesive composition may also contain heat stabilizers such as alkyl substituted phenols, phosphites, sebacates and cinnamates. When present, preferred heat stabilizers are the organic phosphites disclosed in U.S. Patent No. 6,512,033, which is incorporated herein by reference. The heat stabilizer may constitute at least 0.01% by weight or at least 0.3% by weight, at most 5% by weight, at most 2% by weight or at most 1.0% by weight, based on the total weight of the adhesive composition. The adhesive composition may not contain such a heat stabilizer.

The composition of the present invention may further comprise a UV light absorber (UV light stabilizer). Useful UV light absorbers include benzophenone and benzotriazole. Particular UV light absorbers are BASF products such as TINUVIN (TM) P, 2- (2'-hydroxy-5'-methylphenyl) -benzotriazole; TINUVIN ™ 326, 2- (5-chloro-2H-benzotriazol-2-yl) -6- (1,1-dimethylethyl) -4-methylphenol; TINUVIN ™ 213 poly (oxy-1,2-ethanediyl), (α (3- (3- (2H-benzotriazol- Phenyl) -1-oxopropyl-omega -hydroxy, poly (oxy-1,2-ethanediyl), (?, 3- (3- (AH-benzotriazol- (1-dimethylethyl) -4-hydroxyphenyl) -1- oxopropyl) -? - (?, 3- (3- (2H-benzotriazol- (3,5-di-tert-butyl-2-hydroxyphenol) -5-chlorobenzotriazole, TINUVIN ™ 571, branched and linear 2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol; TINUVIN ™ 328, 2- (2H-benzotriazol- , 6-bis (1,1-dimethylpropyl) phenol, and Cytec products such as CYASORB ™ UV-9, 2-hydroxy-4-methoxybenzophenone, CYASORB ™ UV-24, 2,2'- 4-methoxybenzophenone, CYASORB ™ UV-1164, - [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin- ) Phenol; CYASORB ™ UV-2337, 2- (2 ' -Hydroxy-3'-5'-di-t-amylphenyl) benzotriazole, CYASORB ™ UV-2908, 3,5-di- -5337, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole; CYASORB ™ UV-531, 2-hydroxy- Benzophenone, and CYASORB ™ UV-3638, 2,2- (1,4-phenylene) bis [4H-3,1-benzoxazin-4-one] 4-n-octoxybenzophenone, and branched and linear 2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol are preferred. 0.1% by weight or more, 0.2% by weight or more, or 0.3% by weight or more of the weight, and 3% by weight or less, 2% by weight or 1% by weight or less thereof.

The adhesive composition of the present invention may further comprise one or more light stabilizers. Preferred light stabilizers include hindered amine light stabilizers such as TINUVIN 144, n-butyl- (3,5-di-tert-butyl-4-hydroxybenzyl) bis- (1,2,2,6- -Piperidinyl) < / RTI >malonate; Dimethyl succinate polymer with TINUVIN (TM) 622, 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol; TINUVIN (TM) 77, bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate; TINUVIN ^TM 123, bis- (1-octyloxy-2,2,6,6, tetramethyl-4-piperidinyl) sebacate; TINUVIN (TM) 765, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate; CHIMASSORB ™ 944 poly [[6- (1,1,3,3-tetramethyl-butyl) amino] -1,3,5-triazine-2,4-diyl] [(2,2- 6,6-tetramethyl-4-piperidinyl) imino] -1,6-hexanediyl [(2,2,6-tetramethyl-4-piperidinyl) imino]]); CYASORB ™ UV-500, 1,5-dioxaspiro (5,5) undecane 3,3-dicarboxylic acid, bis (2,2,6,6-tetramethyl-4- Ridinyl) esters; (2,2,6,6-tetramethyl-4-piperidyl-pyrrolidine-2,5-dione) and CYASORB ™ UV-3346, poly [ (6-morpholino-s-triazine-2,4-diyl) [2,2,6,6-tetramethyl-4-piperidyl) imino] -hexamethylene [ 6-tetramethyl-4-piperidyl) imino]]. Of these, bis- (1-octyloxy-2,2,6,6, tetramethyl-4-piperidinyl) sebacate and bis (1,2,2,6,6-pentamethyl- Decyl) sebacate is the preferred type. The light stabilizer (s) may constitute at least 0.1 wt.%, At least 0.2 wt.% Or at least 0.3 wt.% Of the adhesive composition and may constitute up to 3 wt.%, 2 wt.% Or 1.5 wt. .

The adhesive composition of the present invention may further comprise a hydrophilic substance which functions to draw atmospheric moisture into the composition. This material enhances the rate of curing of the formulation by attracting atmospheric moisture to the composition. Preferably, the hydrophilic material is a liquid. Among useful hydrophilic materials are pyrrolidines, such as 1-methyl-2-pyrrolidone (or N-methylpyrrolidone). Other hydrophilic materials include ethylene oxide containing polyether polyols and amine group containing catalytically active polyols which may be present as separate components or may be used as polyol components in the prepolymer preparation described above. When added as a separate component, the hydrophilic material may constitute at least 0.1 wt% or at least 0.3 wt% of the total weight of the adhesive composition, and may constitute 1.0 wt% or less or 0.6 wt% or less of the total weight of the adhesive composition.

Optionally, the composition may further comprise a thixotrope (rheological additive). Such stabilizers are well known to those skilled in the art and include dry silica, treated silica, and the like. The thixotropic agent may constitute at least 0.1 wt% or at least 1 wt%, at most 10 wt%, or at most 2 wt% of the adhesive composition.

The various components of the adhesive composition are preferably combined under an inert atmosphere in the absence of oxygen and atmospheric moisture to prevent premature reaction. Preferably, the materials are blended under vacuum or an inert gas, such as nitrogen or argon. Any amount of plasticizer that is not added during prepolymer formation may be added if the prepolymer is blended with other components of the adhesive. The components are blended for a time sufficient to produce a well blended mixture, preferably from about 10 to about 60 minutes. Preferably, the components are blended at a temperature of from about 25 [deg.] C to about 90 [deg.] C. Once the adhesive composition is formulated, it is packaged in a suitable container to protect it from atmospheric moisture and oxygen.

The viscosity of the adhesive composition can be expressed in terms of the press flow viscosity, in which the amount of time (20 seconds) the adhesive composition passes through the hole of 4.0 mm under an applied pressure of 552 kPa at 23 캜. The press flow viscosity may be, for example, at least 5 seconds, at least 10 seconds, at least 20 seconds, or at least 25 seconds, for example at most 200 seconds, at most 100 seconds, or at most 60 seconds. In some embodiments, the amount of plasticizer is selected such that the press flow viscosity of the adhesive composition is within this range.

The compositions of the present invention are useful for bonding substrates that may be porous or non-porous. The composition is applied to a first substrate, and the composition on the first substrate is then contacted with a second substrate. The composition is then exposed to curing conditions that generally involve the presence of moisture. The moisture can be atmospheric moisture and / or liquid water. The curing may be carried out under ambient conditions, such as ambient humidity and temperatures of, for example, 40 DEG C or less. High temperatures may be applied to promote curing.

In a preferred embodiment, one substrate is glass or transparent plastic coated with a wear resistant coating, and the other substrate is a plastic, metal, glass fiber, or composite substrate that can be selectively painted or coated. The plastic coated with the abrasion resistant coating may be any clear plastic, such as polycarbonate, acrylic, hydrogenated polystyrene or hydrogenated styrene conjugated diene block copolymer, having a styrene content of greater than 50%. The coating may comprise any coating that is abrasion resistant, such as a polysiloxane coating. Preferably, the coating has an ultraviolet-tinted light-blocking additive. Preferably, the glass or coated plastic window has an opaque coating located in the area in contact with the adhesive to prevent UV light from reaching the adhesive. This is commonly referred to as frit. Preferably, the opaque coating is an inorganic enamel or an organic coating.

In a preferred embodiment, the composition of the present invention is applied to the surface of glass or coated plastic along with a portion of the glass or coated plastic to be bonded to the structure. The composition is then contacted with the second substrate such that the layer of adhesive composition is located on the line of adhesion between the glass or coated plastic and the second substrate. The composition is cured to form a durable bond between the glass or coated plastic and the substrate.

In another embodiment, the composition is applied to the surface of another substrate and then contacted with the described glass or coated plastic. Adhesive is applied as a bead around a window positioned so that when the adhesive is placed in a vehicle, the adhesive contacts the window flange. The window over which the adhesive is placed is then placed into the flange with the adhesive positioned between the window and the flange. The adhesive bead is preferably a continuous bead functioning to seal the joint between the window and the window flange. The continuous bead of adhesive is a bead positioned such that the bead is connected at each end to form a continuous seal between the window and the flange upon contact. Thereafter, the adhesive is cured.

In one embodiment, the compositions of the present invention are used to replace windows in a structure or vehicle, and most preferably in a vehicle. The first step is to remove the previous window. This can be accomplished by cutting the adhesive bead that holds the old window in place and then removing the old window. Then, prepare a new window by wiping it. The old window can be removed by cutting out the old adhesive located on the window flange. Older adhesives can be applied by applying the adhesive of the present invention over a thin layer of an old adhesive that remains attached to the structure or vehicle, although the adhesive of the present invention can be applied and removed before the new window is assembled onto the vehicle or structure It is common. The window flange is preferably primed with a paint primer. The window over which the adhesive is placed then contacts the window flange as described above. In another embodiment, the adhesive may be applied to the window flange instead of the window.

In another embodiment, the compositions of the present invention may be used to bond modular components together. Examples of modular components include vehicle modules, such as doors, windows or bodywork.

The adhesive composition of the present invention preferably exhibits a lap shear strength of at least 2.76 MPa (400 psi) after curing for 7 days at 23 ° C and 50% relative humidity. The adhesive composition of the present invention preferably exhibits a Young's modulus of at least 3 MPa as measured according to ASTM D412 (Die C) after curing under the same conditions.

 The adhesive composition of the present invention exhibits an increase in press flow viscosity of not more than 100%, more preferably not more than 50%, after being aged under nitrogen for 3 days at 65 占 폚 before curing.

 The adhesive composition of the present invention exhibits excellent heat and hydrolytic stability. The hydrolysis and thermal stability can be evaluated by evaluating the fracture properties of the cured adhesive after the substrate adhered by the cured adhesive as described in the examples is immersed in water at 90 캜 for several hours. The cured adhesive preferably exhibits a 100% cohesive failure mode when it is evaluated using the adhesion test described in the following examples after immersion in water at 90 DEG C for at least 10 days.

The following examples are provided to illustrate the invention, but do not limit the scope of the invention. Unless otherwise indicated, all parts and percentages are by weight.

In the following examples:

VORANOL 220-056N POLYOL is a nominally difunctional, poly (propylene oxide) having a hydroxyl number of 56 (equivalent 1000) available from The Dow Chemical Company.

VORANOL 232-036N POLYOL is a nominally trifunctional poly (propylene oxide) with a hydroxyl number of 36 (equivalent 1558) available from The Dow Chemical Company.

Polyester polyols are commercially available from Evonik as Dynacoll (TM) 7381.

Diisononyl phthalate is a plasticizer available from UPC Technology.

MDI is methylenediphenyl diisocyanate (isocyanate equivalent 125, isocyanate functionality 2.0) available from The Dow Chemical Company as Isonate 125M.

Polymeric MDI is commercially available from The Dow Chemical Company as PAPI ™ 20. It has an isocyanate functionality of 3.2 and an isocyanate equivalent of about 138.

Metacure ™ T-9 is a tin octoate urethane catalyst available from Air Products.

Diethyl malonate is a commercially available product from Parchem Fine & Specialty Chemicals, New Rochelle, NY, USA.

The trimerized hexamethylene diisocyanate is Desmodur ™ N3300 from Covestro. It has an isocyanate functionality of greater than 2.5 and an isocyanate content of 21.8% (isocyanate equivalent of about 193).

The dimorpholonodiethyl ether catalyst is Jeffcat DMDEE catalyst from Huntsman.

The dimethyltin dineodecanoate catalyst is a Fomrez 占 UL-28 catalyst from Momentive Performance Materials.

Mercaptosilane is a gamma-mercaptopropyltrimethoxysilane commercially available as Silquest A-189 from Momentive Performance Materials.

Aminosilane is a commercially available bis- (gamma-trimethoxysilylpropyl) amine as Silquest ^TM 9627 from Momentive Performance Materials.

The epoxy silane is gamma-glycidoxypropyltrimethoxysilane, commercially available as Silquest ^TM A-187 from Momentive Performance Materials.

Trinonyl phenyl phosphite is commercially available as Doverphos (R) 4 from Dover Chemical.

UVA absorber A is Tinuvin 571 from BASF.

The light stabilizer is Tinuvin® 765 from BASF.

Calcium carbonate is available from J.M. HUBERCARB ™ Q325 available from Huber.

BETASEAL ™ 43518 is a silane-containing clear glass primer from Dow Chemical Co.

BETASEAL (TM) 43520A is an isocyanate-containing black glass primer from Dow Chemical Co.

BETASEAL ™ 43526 is a silane-containing black glass primer from Dow Chemical Co.

BETAPRIME ™ 5500 is an isocyanate-containing black glass primer from Dow Chemical Co.

Example 1 and Comparative Sample A-C

A. Preparation of prepolymer solution 1

363.68 g of Voranol 220-056 polyol, 527.04 g of Voranol 232-036 polyol and 32 g of diisononyl phthalate are charged into a 4 liter kettle, mixed and heated to 54 DEG C under nitrogen. All subsequent steps are performed under nitrogen. Add 160.64 g of molten MDI and mix. 0.08 g of tin octoate catalyst is added dropwise. The temperature of the kettle rises due to the heat of reaction; The reaction mixture is maintained at 80 < 0 > C to 90 < 0 > C for 30 minutes. Thereafter, the reaction mixture is cooled to 60 DEG C, 501.20 g of diisononyl phthalate and 15.36 g of diethyl malonate are added, mixed for 30 minutes, and then cooled to room temperature. The resulting prepolymer solution 1 had an isocyanate content of 1.25 wt% and a viscosity of 16,000 cps at 23 DEG C, as measured according to the procedure set forth in US Pat. No. 5,922,809, column 12, lines 38 to 49.

B. Preparation of Example 1 and Comparative Samples A, B and C

210 g of calcium carbonate, 61.25 g of clay and 372.75 g of EfltexTM S7100 carbon black are mixed and dried at 200 DEG C for about 20 hours and then cooled in a closed vessel to form a filler mixture. Elftex carbon black has an oil absorption of 117 cc dibutyl phthalate per 100 g.

Separately, 1045.28 g of prepolymer solution 1, 1.35 g of trimerized hexamethylene diisocyanate, 3.8 g of dimorpholono diethyl ether catalyst, and 2.63 g of a 10% solution of dimethyltin dinneodecanoate catalyst in diisononyl phthalate were mixed with 2 Charge into a gallon mixer. The mixture is degassed and mixed under vacuum for 5 minutes. Vacuum is removed using nitrogen and then 8.75 g of mercaptosilane are added, followed by degassing and mixing under vacuum for 10 minutes. The vacuum is again released using nitrogen and then the filler mixture is added into the mixer. Thereafter, the vacuum is gradually applied. When half of the vacuum is achieved, mixing is initiated and the filler is allowed to wet for 2 minutes. Thereafter, the vacuum valve is fully opened and further mixing is continued in a full vacuum for 15 minutes. The mixture is then scraped off and 10.5 g of trinonyl phenyl phosphite is added and mixed under vacuum for 10 minutes. The obtained adhesive composition (Example 1) was packed in an airtight tube, which was stored in a sealed aluminum bag filled with nitrogen.

The press flow viscosity for an adhesive sample is measured by measuring the amount of time (in seconds) that 20 grams of adhesive composition passes through a 4.0 mm hole under conditions of 552 kPa applied pressure at 23 DEG C, unless otherwise specified. The press flow viscosity of Example 1 is 30 seconds. After aging the adhesive composition of Example 1 at 54 占 폚 under nitrogen for 3 days, the press flow viscosity increases only slightly to 35 seconds.

Deflection performance is measured by the following method. A metal panel with a height of 10 cm and a length of 30 cm is placed vertically on the longest side. The right triangle beads of the adhesive composition having a height of 1.8 cm and a base of 0.6 cm are distributed along the top edge of the panel with the bead height perpendicular to the panel. After 30 minutes, measure the amount of deflection or drop of the adhesive bead tip in millimeters. Example 1 does not show measurable deflection. After aging the adhesive of Example 1 at 54 占 폚 under nitrogen for 3 days, the adhesive still does not exhibit deflection in this test.

Comparative Sample A was prepared in the same manner except that mercaptosilane was replaced by the same weight of aminosilane.

Comparative Sample B was prepared in the same manner as in Example 1, except that mercaptosilane was replaced by an equal weight of epoxy silane.

Comparative Sample C was prepared in the same manner as in Example 1, except that the dimethyltin dinneodecanoate catalyst solution was replaced with the same amount of prepolymer solution 1.

The rounded patties of Example 1 and Comparative Samples A and B were cured for 7 days at 23 ° C and 50% relative humidity. Test coupons were cut from these cured sample patties and tested for tensile strength, elongation and Young's modulus (1 to 10% elongation) according to ASTM D412 (Die C). The results are shown in Table 1 below. The hardness is measured according to ASTM D2240.

* Not an example of the present invention.

The peel adhesion samples of Example 1 and Comparative Samples A and B were prepared as follows: Triangle beads having 6.3 mm bottom, 12 mm height and 100 mm length were immersed in a bismuth enamel glass coupon with a BETAPRIME (TM) mm x length 150 mm). The beads are pressed against the release paper to a thickness of 3 mm, which is then cured for 5 days at 23 DEG C and 50% relative humidity. The peel adhesion samples were then immersed in a 90 ° C hot water bath before testing for 5 days, 7 days, 10 days and 12 days, respectively. All peel adhesion samples are prepared and tested twice for each adhesive sample and for each test condition.

At the time of testing, a slit (20-40 mm) is cut between the adhesive bead end and the substrate. The cured bead is then cut through the substrate tested at a 60 degree angle using a razor blade, pulling the end of the bead back at an angle of> 90 degrees. And cut in a notch shape every 3 to 5 mm above the substrate. Adhesion is evaluated by adhesive breakage (AF), thin film breakage (TF) and / or cohesive failure (CF). In the case of AF, the cured bead can be separated from the tested substrate surface, whereas in CF the separation occurs in the sealant adhesive as a result of cutting and pulling, and TF is the temperature at which a thin film of adhesive, It is a special case of CF that will remain. The results are shown in Table 2 below.

Hot-water aged peel adhesion results on a bismuth enamel glass panel coated with BETAPRIME ™ 5500 glass primer

The peel adhesion test is performed in the same manner on a bismuth enamel glass panel primed with BETASEAL (TM) 43526. The results are shown in Table 3 below.

Hot water aged peel adhesion results on bismuth enamel glass panel coated with BETASEAL ™ 43526 glass primer

The peel adhesion test for Example 1 is performed on a freshly coated metal panel with Gen ™ V paint without a paint primer. Example 1 shows 100% CF on Gen V paint. If the comparative sample C is evaluated in the same way, the failure mode is only 10% CF. These results demonstrate the advantage of using a mixture of a dimorpholino diethyl ether catalyst and a metal containing catalyst.

The lap shear adhesion of Example 1 is evaluated according to the SAE J1529 test procedure. Triangle beads having a base of approximately 6.3 mm and a height of 8 mm were applied along the width of a 25 mm x 100 mm bismuth-zinc fritted glass primed with both Betaseal ™ 43518 and Bentaseal ™ 43520A, Make a sample. The e-coated metal coupon is pressed directly onto the adhesive bead to form an overlap of adhesive beads of 6.3 mm and 6.3 mm thickness between the substrates. The samples are cured for 3 days at 23 < 0 > C and 50% relative humidity. One sample is then immediately evaluated for wrap shear strength at a pull rate of 50 mm / min. Another sample is further aged at 40 < 0 > C and 100% relative humidity for 14 days. The results are shown in Table 4 below.

The results of the lap shear adhesion of Example 1

Examples 2 and 3

Example 2 is prepared in the same general manner as in Example 1 from the following components:

ingredient weight%

The prepolymer solution 56.33%

Diisononyl phthalate 3.0%

Polymer MDI 2.0%

Trimerized hexamethylene diisocyanate 2.0%

Dimorpholinoether 0.217%

Dimethyltin Dineodecanoate

(10% in diisononylphthalate) 0.15%

Mercaptosilane 0.5%

Elftex ™ S7100 Carbon Black 22.7%

clay 3.5%

CaCO ₃ 9.0%

Trisnonylphenylphosphite 0.6%

Example 3 is prepared in the same manner except that carbon having an oil absorption of only 72 cc dibutyl phthalate per 100 g (Monarch ™ 120, Cabot Corporation) is used instead of Elftex ™ carbon.

Example 2 shows an initial press flow viscosity of 48 seconds. When this is subjected to thermal aging treatment at 54 占 폚 for 3 days, its press viscosity does not change. Example 2 does not exhibit deflection when evaluated before and after thermal aging for 3 days at 54 ° C. Its Young's modulus (1 to 10% elongation) is 8.76 MPa. The tensile strength is about 9000 kPa (1300 psi) and the elongation is 248%. Shore A hardness is 81.

 Example 3 shows an initial deflection of 20 mm in the deflection test. The results of Example 2 and Example 3 demonstrate the advantage of using carbon black with high oil absorption together with mercaptosilane.

Example 4 and Comparative Sample D

Example 4 is prepared in the same general manner as in Example 1 from the following components:

ingredient weight%

Prepolymer solution 1 56.93%

Diisononyl phthalate 2.6%

Polymer MDI 1.0%

Trimerized hexamethylene diisocyanate 2.0%

Dimorpholino diethyl ether 0.17%

Dimethyltin Dineodecanoate  

(10% in diisononylphthalate) 1.0%

Mercaptosilane 1.6%

Elftex ™ S7100 Carbon Black 21.2%

clay 13.0%

UVA absorbent A 0.5%

Comparative Sample D was prepared in the same manner except that mercaptosilane was replaced by the same weight of aminosilane.

Example 4 does not show sag in the sag test after aging for 3 days at 65 ° C. After the same thermal aging condition, Comparative Sample D exhibits deflection of 9 mm in the test and the entire coated bead slides down to about 1 mm, which is a very bad result.

Example 4 has an initial press viscosity of 43 seconds, which increases to about 51 seconds after aging for 3 days at 65 占 폚. Example 4 has a viscosity heat increase of 18.6%. Example 4 has much better rheological stability than Sample D.

Example 5

A. Prepolymer solution 2

280 g of diisononyl phthalate is placed in a reaction vessel under nitrogen and heated to 50 占 폚. After adding 172.8 grams of molten MDI and mixing, 1147.2 grams of the molten polyester polyol is gradually added. The obtained reaction mixture is reacted under nitrogen at 80 to 90 DEG C for 40 minutes, and then the obtained prepolymer solution 2 is stored in an airtight drying vessel. Prepolymer solution 2 is a solid at room temperature and has an isocyanate content of 2.0% by weight.

B. Preparation of Example 5

128 g of calcium carbonate, 56 g of clay and 348 g of Efltex 占 S7100 carbon black are mixed and dried at 200 캜 for about 20 hours and then cooled in a sealed vessel to form a filler mixture.

Separately, the mixer vessel is first heated to 65 ° C using a heating jacket. Thereafter, 963.04 g of prepolymer solution 1, 12.8 g of MDI, 40 g of trimerized hexamethylene diisocyanate, 0.96 g of dimorpholono diethyl ether catalyst and 10% dimethyl tin dinneodecanoate catalyst in diisononyl phthalate Fill 19.2 g and mix together under vacuum for 5 minutes. Then, 12.8 g of mercaptosilane are added into the mixer and mixed under vacuum for 10 minutes. The vacuum is released using nitrogen and the filler mixture is added. Thereafter, the vacuum is gradually applied. When half of the vacuum is achieved, mixing is initiated and the filler is allowed to wet for 2 minutes. Thereafter, the vacuum valve is fully opened and further mixing is continued under full vacuum for 15 minutes. The mixture was then scraped off and 1.39 g of each of UVA absorbent A and light stabilizer, 1.22 g of trinonyl phenylphosphite and 14.4 g of molten prepolymer solution 2 were added and mixed under vacuum for an additional 10 minutes. The obtained adhesive composition (Example 5) is packed in a tube.

Example 5 has an initial press flow viscosity of 47 seconds, which increases to only 51 seconds after aging Example 5 at 54 DEG C for 3 days. Example 5 does not show deflection before or after thermal aging treatment. After curing for 7 days at 23 ° C and 50% relative humidity, Example 5 exhibits a tensile strength of 7880 kPa (1,143 psi), an elongation of 286%, a Young's modulus of 6.21 MPa and a Shore A hardness of 76.

Claims (14)

A urethane prepolymer resin, a reactive silane, a polyisocyanate having a functionality of greater than 2, at least one catalyst for isocyanate reaction with a hydroxy group; And a carbon black filler. The adhesive composition of claim 1, wherein the reactive silane is mercaptosilane. Wherein the reactive silane is added separately to the composition during mixing of the various components of the adhesive composition.  4. The method of claim 3, wherein the reactive silane is mercaptosilane. An adhesive composition prepared from any one of the manufacturing methods of claim 3 or 4. a) an isocyanate-terminated prepolymer having a free isocyanate group and an isocyanate equivalent of 840 to 5,000;
b) 0.1 to 6 parts by weight of at least one polyisocyanate compound per 100 parts by weight of the moisture curable adhesive composition, having an isocyanate equivalent of 300 or less and a number average number of isocyanate functionality of 2.5 or more;
c) from 0.1 to 4 parts by weight of at least one hydrolyzable organosilane comprising 100 parts by weight of a mercaptosilane having one mercapto group and at least one hydrolyzable silane group per 100 parts by weight of the moisture curable adhesive composition;
d) at least one urethane catalyst, and
e) a carbon black filler. 7. The adhesive composition of claim 6, wherein the mercaptosilane comprises at least one mercaptoalkyl (trialkoxy) silane or mercaptoalkylmethyl (dialkoxy) silane. The adhesive composition according to claim 6 or 7, wherein the carbon black has an oil absorption number of at least 80 cm 3 of dibutyl phthalate per 100 g of the carbon black as measured according to ASTM D-2414-09. The adhesive composition according to any one of claims 6 to 8, wherein the isocyanate-terminated prepolymer comprises at least one reaction product of a polyether diol and a diisocyanate. The adhesive composition according to any one of claims 6 to 9, wherein the isocyanate-terminated prepolymer comprises at least one reaction product of a polyester diol and a diisocyanate having a melting temperature of 40 to 85 ° C. The adhesive composition according to any one of claims 6 to 10, further comprising a plasticizer. The adhesive composition according to any one of claims 6 to 10, which exhibits a press flow viscosity at 23 占 폚 for 5 to 200 seconds. A) forming an isocyanate-terminated prepolymer;
B) mixing the isocyanate-terminated prepolymer with at least one hydrolyzable silane; And thereafter
C) combining at least one polyisocyanate compound having an isocyanate equivalent of 210 or less, a urethane catalyst and a carbon black with a mixture of said isocyanate-terminated prepolymer and said at least one hydrolyzable silane. Lt; RTI ID = 0.0 > 1, < / RTI > A) forming an isocyanate-terminated prepolymer;
B) mixing the isocyanate-terminated prepolymer with at least one polyisocyanate compound having an isocyanate equivalent of 210 or less; And thereafter
C) combining at least one hydrolysable silane, urethane catalyst and carbon black with a mixture of said isocyanate-terminated prepolymer and said at least one hydrolyzable silane. A process according to any one of claims 6 to 12, Gt;